Acidyl polyalkylene polyamines



scrum PGLYALKYLENE PULYS Wilhelm Neelmeier, Theodor Nocken, and Her-Friedrich, 'Leverkusen-on-the-e,

Germany, assignors, by mesne assignments, to General Aniline Works, Inc,New York, N. Y

a corporation cit Delaware his thawing. Application May 27, 19%, SerialNo. 56,286, and in Germany May 1929 7 26' carat. (ci. 260-12431 Thepresent invention relates to new condensation products from higheraliphatic acids and polyalkylene polyamines and to a process ofpreparing same, more particularly it relates to condensation productswhich may be represented by the probable general formula:

Y-C0--NH-A--Z wherein A represents the group flint-311E1- NH- of whichthere are two or more serially arranged, R and R1 standing for hydrogenor methyl, wherein Y stands for an aliphatic" hydrocarbon radical,preferably one containing at least 9 carbon atoms, which hydrocarbonradical may contain one or more double bonds and may be substituted byhydroxy groups, that is, the grouping Y-CO stands for the acidyl radicalof a saturated or unsaturated fatty acid or hydroxy fatty acid, forexample, a radical of lauric acid, palmitic acid, stearic acid, oieicacid, ricinoleic acid, Z stands for hydrogen or an aliphatic acidylradical derived from a saturated or unsaturated fatty acid, preferablyone containing at least 10 carbons atoms which may be substituted byhydroxy groups.

The preferred condensation products, may be represented by the formula:

CHR1-NHZ wherein Y, R and R1 are defined as above and Z stands forhydrogen, an aliphatic acidyl,-CHR. -CHR1NH2 0r -CI-IR-CHR1NH- aliphaticacidyl in which the his are defined as above and the aliphatic acidyl isderived from a, saturated or unsaturated fatty acid which maybesubstituted by hydroxy groups, preferably such an acid as contains atleast 10 carbon atoms.

wherein A is defined as above for example, diethylene triamine:NH2-C2H4-NH-C2H4 NHz, dipropylene triamine:

and a higher aliphatic saturated or unsaturated fatty acid, preferablysuch a one as contains at least 10 carbon atoms, or an ester of such afatty acid, for example, the ethyl esters or advantageously theglycerides as occurring in nature, such as animal and vegetable fats andoils.

The quantities of the two components reacting upon each other may bevaried within the widest limits, but generally it is best to work withan excess of the base, say with'double the calculated quantity or more.When starting with the free aliphatic acid, the reaction is preferablycarried out by mixing together the two componentsat room temperature anddistilling oii the excess of amine and water formed in vacuo, say undera pressure of about 10 mm. When starting with the esters of thealiphatic acids the reaction mixture is heated for several hours, say2-4 hours, to 130-250 (3., thenthe excess of base and the alcohol formedare distilled off under reduced pressure.

A preferred method of carrying out our process isachieved by startingwith the mixture of bases obtainable by heating -120 C. ethylenechloride with ammonia under pressure and distilling off the ethylenediamine formed, said mixture containing piperazine besides the amines 80having chain form.

According to our process there is obtained a mixture of monoacidylpolyalkylene polyamines and diacidyl polyalkylene polyamines. The twocomponents can be separated by fractional crystallization from alcohol,the diacidyl product being more difficultly soluble than the monoacidylproduct. The best method of separating the two reaction products is byusing diluted hydrochloric acid in which the monoacidyl product issoluble, the diacidyl product being insoluble or scarcely solubletherein.

Our new products are oily or solid substances, the monoacidyl productsbeing soluble in-dilute hydrochloric acid, acetic acid, alcohol, fat,such as linseed oil, insoluble or sparingly soluble in water, insolublein alkalies; thediacidyl compounds are insoluble in dilute hydrochloricacid, water and alkalies, soluble in hot alcohol. The

monoacidyl product as well as the mixtures of the monoand di-acidylproducts yield strongly lathering solutions in diluted hydrochloric andacetic acid. Our new products are valuable intermediate substances inthe manufacture of wetting agents, some of them being used as suchimmediately.

The invention is illustrated by the following examples, without beingrestricted thereto:

Example 1.--100 parts by weight of oliye oil and 100 parts by weight ofdiethylenetriamine are heated to about ISO-200 C. until a test portionof the reaction mixture is soluble in dilute hydrochloric acid. Afterdistilling off the excess of diethylene-triamine, advantageously underreduced pressure, there remains a strongly viscous mass, thehydrochloric acid solution of which has great foam forming properties.

A similar product is obtainable by heating free oleic acid with a largeexcess of diethylene-triamine under the same conditions.

Example 2,-310 parts by weight of the ethylester of oleic acid areheated with 286 parts by weight of triethylenetetramine. at about 160 C.for 12 hours when a homogeneous solution is formed; the alcohol formedand the excess of triethylenetetramine are distilled oiT. The residualreaction product forms a brown oil, which is diflicultly soluble inwater and readily soluble in alcohol, benzene and dilute hydrochloricacid.

A quite similar product is obtainable by heating free oleic acid with anexcess of triethylenetetramine to about l80-200 C. and distilling offthe excess of triethylenetetramine under reduced pressure.

Ea:ample 3.-200 parts by weight'of olive oil are heated at 180-200 C.with 300 parts by weight of a mixture of bases, which is obtained by theaction of ammonia on ethylene chloride at 80- 120 C. under pressure ofatm. and after distilling off the ethylene diamine said mixture of basesboiling at about 15 mm mercury between 90 and 300 C. When a test portionof the reaction product is smoothly soluble in dilute hydrochloric acidthe water formed and the excess bases are distilled off under reducedpressure and a yellowish brown oil is obtained, a solution of which indilute hydrochloric acid can be used as a washing or wetting agent.

Ewample 4.-Eo ual parts by weight of stearic acid andtriethylene-tetrami-ne are heated at zoo-210 0. (oil bath temperature)until a test of the reaction product is soluble in dilute hydrochloricacid. After distilling off the excess triethylenetetramine there remainsa nearly colorless mass which solidifies after cooling, being soluble inalcohol and dilute hydrochloric acid. The hydrochloric acid solutionshows pronounced foam forming properties.

Instead of stearic acid other higher fatty ac ids, for example linseedoil, ricinoleic acid, acids of wool fat and the like, may be used.

Example 5.--Equa1 parts of linseed oil and the mixture of bases(described in Example 3) are heated for about 5 hours to 200-205 (oilbath temperature) and the excess free bases and the glycerine formedduring the reaction are distilled oil under reduced pressure. Theremaining oil is easily soluble in dilute hydrochloric acid and showsgood foaming and emulsifying properties.

Instead of linseed oil also other fats, for example, train oils, w'oolfat, beef fat and the like may be used.

We claim:

1. The process which comprises causing one molecular proportion of acompound of the group consisting of higher aliphatic fatty acids andesters thereof and at least two molecular proportions of a polyalkylenepolyamine of the general formula:

wherein R. and R1 stand for hydrogen or methyl and X stands for hydrogenor --CHR-CHR1NH2 in which the R's are de---chloride at 80-420 0. under apressure of 10 atm.

wherein R and R;

fined as above, to react upon each other at elevated temperature.

' 2. The process which comprises causing one molecular proportion of anester of a higher aliphatic acid and at least two molecular proportionsof a polyalkylene polyamine of the general .for'mula:

stand for hydrogen or methyl and X stands for hydrogen or --CH'R-CHR1NH2in whichthe Rs are defined as above to react upon each other for severalhours at a temperature between 130 and 250 C.

4. The process which comprises causing one molecular proportion of anester of a monobasic higher aliphatic acid, the acid containing l6-18carbon atoms, and at least two molecular proportions of a polyalkylenepolyamine of the general formula:

wherein X may be hydrogen or -CH2CH2NH2, to react upon each other forseveral hours at a temperature between 130 and 250" C.

5. The process which comprises causing one molecular proportion of aglyceride of a monobasic higher aliphatic acid, the acid containing16-18 carbon atoms, and at least two molecular proportions of apolyalkylene polyamine of the general formula:

wherein X may be hydrogen or ---CHa-CH2-NH2, to react upon each otherfor several hours at a. temperature between and 250 C.

6. The process which comprises heating one molecular proportion oflinseed oil with at least two molecular proportions of a polyalkylenepolyamine of the general formula:

wherein X may be hydrogen or CH2-CH2-NH2, to react upon each other forseveral hours at a temperature between 130 and 250 C.

7. The process which comprises causing an ester of a monobasic higheraliphatic acid, the acid containing 16-18 carbon atoms, and an aboutequal part by weight of the mixture of bases'obtained by the action ofammonia on ethylene chloride at 80-120 C. under a pressure of 10 atm.and distilling off the ethylene diamine, to react upon each other forseveral hours at a temperature between 130 and 250 C.

8. The process which comprises causing a glyceride of a monobasic higheraliphatic acid, the acid containing 16-18 carbon atoms, and an aboutequal part by weight of the mixture of bases obtained by the action ofammonia on ethylene Lil!) enten {Ie sdmnmnge1i-the ,aa ae mme to react 1ethylene, chloridefat' six-.120 petimer a ti ssure fllvherein' R and R1stand'for hydrogen formethyl,

stands-ror an aliphatic-hydrocarbon radic 'Icontaining= at' leastl9carbon atoms -lwh h-.-may 'cont'ain' dcubleibonds and which may-;, ;besubstituted by 'hydroxy groups: and ,z stands-for hydro:

t eka t rie ?enda w' v I flgf'rheprocess?whichgcomprises causing 1 1oatmian'd distillin'goflthei'ethyleric a to upon each' emeritus-severalfhjours: t be 'ewfeihe w e io-endzsoic v a ids suspen ers. s r e ed-l se! wa gen, an aliphatic, acldyl, -CHR,CHR1 -NHz or.

1 I-CHRCHR. -NH-'-aliphaticaeidy'l fwhich the .R's are'deflned as aboveand thealphatic. acidyl is derived from a saturated or unsaturated.

fatty acid which may be substituted by hydro'x'y j j groups,said-i1 acidcontaining at least 10 carbon ,-'atpms,"said pro'ducts being. oily orsolid substan l'fces, the, monoacidyl products being soluble infpoundsibeing-soluble inhotalcohol, insoluble in hydrochloric; acid,alkalies and water, being vval- ,uable wetting agents or intermediateproducts 'f'in the manufacture of wetting agents.

11.-Condensation', products from higher ali- .jphatic- IattyEacids andpolyallrylene polyamines "for the probable general formula:

" ;manu1acti1re of wetting agents.

} wherein R andRi stand for hydrogen or methyl,

"11' stands for an aliphatic hydrocarbon radical containingl'at least 9carbon atoms which may ,fcntain-,,double= bonds and which may besubstituted b'y hydroxy groups, and wherein-z stands fon hydrogen or-CHR--CH R1NH: in which R and R1 are defined-as above, said productsbeing oily orsolid'substances, being soluble inv dilute hydrochloricacid, acetic acid, alcohol, fat, insoluble in water and alkalies,being'valuable 'wet ting agents and intermediate products in the12.'Condensation products from higher aliphatic fatty acids andpolyalkylene polyamines 'of the probable general formula:

. I NH.C HR-CHR1Q -NHZ wherein and R1 stand for hydrogen or methyl,

y stands' for an aliphatic hydrocarbon radical containing from 15 to 17carbon atoms which contain double bonds and which may be sub- {sttutedby hydroxy groups, and 2 stands for hygdrogen, an aliphatic acidyl,-CHRCHR.1NH3

Iwhich the 13's are defined as above and th'ali- --phatic acid'yl'isderived from a saturated or.un-'

saturated fatty acid which maybe substituted 1o 16 to 18f carbon atoms,said products beingoilyor.

by groups, said acid 'contain ngfrom 'j solid substances, the monoacidylproducts being 'solublefin ,dilute hydrochloric acid, acetic acid,

" "talcohol', fat, insolubl'in water and alkalies, the diacidyLcompoundsbeing soluble in hot'alcohol,

lfotheritor 'several hours etatemnere:

"partsgbyg Weight of oil 'and-j the --mixture' I R1 are defineda sabove, said pro dilute hydrochloric acid,acetic acid, alcohol, fat,insolublein water and alkalies, the diacidyl com a '3 insoluble in.hydrochloric; acid. alkalies J and watenfb'e n valuable wetting agents'or interme yiiateiu-sproducts in,- the manufacture-or wetting 88 1 1.13.;oouae,nset1o products from ,higher -:ali-

phatic ttyacids and "no yel y ene po m es he robable gfeneral formulas}"Tiers-vacate methyl,

. y stands ,"for'l an aliphatic'ghydrocarbon radical containing from 17;.carbon; atoms a which may "ccntain double bondsj eta which may besubstituted by hydroxy -groups,- z ;stands for hydrogen 'or -.CHR---CHR1-NH; {m which and u tabeingoily olid S bstances, being soluble indflutey chloric ''acid, acetic acid, "alcoholf'fat, insoluble inwater andalka'lies being i valuableww'etting agents and intermediate products inthe mann facturej of wetting agents.

l4. Condensation products from highera11- phatic fatty acids andpolyalkylene polyamines of the probable general fornuflazwherein, ystands for anialiphatic hydrocarbon radical containing from 15 to 1'!carbon atomswhich may contain double bonds and which may be substitutedby hydroxy groups, 2 stands for hydrogen, an aliphatic acidyl, or'phatic acidyl being derived from a saturated or NH-a lipha.tic acidyl,the aliunsaturated fatty acid which may be substituted byhydroxy groupsand which contains from 16 to 18 carbon atoms, said products being oilyor solid substances, the monoacidyl products being soluble in dilutehydrochloric acid, acetic acid,

alcohol, fat, insoluble in water and alkalies, the

diacidyl compounds beingv soluble in hot alcohol,

insoluble in hydrochloric acid, alkalies and water, 4

being valuable wetting agents or intermediate products in themanufacture of wetting agents.

15. Condensation products from higher aliphatic fatty acids andpolyalkylene polyamines of the probable general formula:

wherein 3 stands for an aliphatic hydrocarbon radical containing from-15to 17 carbon atoms which may containdouble bonds'and whichmay besubstitutedby hydroxy being oily or-solid substances, being-soluble indilute; hydrochloric acid,'acetic acid, alcohol, fat, insoluble in waterand alkalies-andbeing valuable wetting agents and intermediate productsin the manufacture or wetting agents. 16. Condensation phatic fattyacids of the probable general formula: c1'lH33CO-NH-C istands forhydrogen or groups, and 2 stands for hydrogenor -'CHs-CHz-N'Hz, saidproducts,

products 'from higher aliand polyallwlene polyamines said productsbeingoily substances, soluble 1 "1'7." As new products,

iii

tr o

of bases, said mixture being obtainable by the action bf ammonia onethylene chloride at '80-120 C. under a pressure of 10 atmospheresandafter distilling oil the ethylene diamine, said mixture of basesboiling at about 15 mm of mercury between about 90 and 300 0.,saidproducts being oily substances, soluble in dilute hydrochloric acid,acetic acid, alcohol, fat, insoluble in waterand alkalies and beingvaluable wetting agents and intermediate products in the manufacture ofwetting agents.

18. As a new product, the condensation product from olive oil and amixture of bases, said mixture being obtainable by the action of ammoniaon ethylene chloride at -120 C. under a pressure of 10 atmospheres andafter distilling ofi the ethylene diamine, said mixture of bases boilingat about 15 mm of mercury between'about and-300 (2., said product beinga yellowishbrown 011, soluble in dilute hydrochloric acid, acetic acid,alcohol, fat, insoluble in water and alkalies and being a valuablewashing or wetting va1uable wetting agents or intermediate 90 and 3000., said product being an oily substance, soluble in dilute hydrochloricacid, acetic acid, alcohol, fat, insoluble in water and alkalies andbeing a valuable washing or wetting, agent.

20. Condensation products of aliphatic fatty? acids and polyalkylenepolyamines of the probable general formula:

' Y--CONH--A--Z wherein A represents the group CHE-CH1;

NHof which there are two or more serially arranged, R and R1 standingfor hydrogen or methyl, wherein Y stands for an aliphatic hydrocarbonradical containing at least 9 carbon atoms which hydrocarbon radical maycontain oneoi' more double bonds and may be substituted by hydroxygroups, and Z stands for hydrogen or they acidyl radical of an aliphaticacid containing at least 10 carbon atoms, being oily or solld'sub-jstances, the monoacidyl products being solubleiin.v

dilute hydrochloric acid, acetic acid, alcohol, fat,"

insoluble in water and. alkalies, and the diacidyl' compounds beingsoluble in hot alcohol, insoluble in hydrochloric acid, alkalies andwater, being products in the manufacture of wetting agents.

WILHELM NEELMEIER'. 1

THEODOR NOCKEN.

HERMANN FRIEDRICH] T

